CN117487164A - Synthesis method of low-viscosity hydroxyl silicone oil - Google Patents
Synthesis method of low-viscosity hydroxyl silicone oil Download PDFInfo
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 47
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000872 buffer Substances 0.000 claims abstract description 18
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 20
- 239000012280 lithium aluminium hydride Substances 0.000 description 7
- -1 lithium aluminum hydride Chemical compound 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a synthesis method of low-viscosity hydroxyl silicone oil, which comprises the following steps: s1, the mass ratio is (28-36): (18-22): (16-20): 1, a buffering agent, a reaction solvent and a first catalyst are mixed and stirred; s2, heating to above 50 ℃, dissolving the hexamethylcyclotrisiloxane, continuously heating to 60-65 ℃, adding a second catalyst, and reacting for 1.8-2.2 hours at a temperature; s3, adding an acetic acid solution to adjust the pH value to be neutral after the reaction is finished; s4, extracting reaction liquid, separating an oil layer, performing low-boiling-point removal treatment on the oil layer, removing impurities, and filtering to obtain a finished product. The hydroxy silicone oil has no color, no smell, and low viscosity (20-30 mm) 2 S), high hydroxyl value (8-12%), and good stability; meanwhile, the buffer acetone, toluene and reaction solvent water used in the synthesis method can be reused, so that the production cost is effectively reduced.
Description
Technical Field
The invention belongs to the field of chemical production, and relates to a synthesis method of low-viscosity hydroxyl silicone oil.
Background
The low-viscosity hydroxyl silicone oil is a structure control agent for preparing a high-performance high-temperature vulcanized silicone rubber material, and currently, the low-viscosity hydroxyl silicone oil used at home refers to hydroxyl silicone oil with the viscosity of 20-35mm < 2 >/s and the hydroxyl content of 6-12%, wherein the hydroxyl content is an important index for judging the quality of the hydroxyl silicone oil, and if the hydroxyl content is too low, the performance and the storage stability of the silicone rubber material are seriously affected. In addition, the low-viscosity hydroxyl silicone oil can be applied to textile emulsifying agents, plastic product additives and the like, and has wide application and high production value.
The current methods for synthesizing low-viscosity hydroxyl silicone oil include acid catalysis, base catalysis and resin catalysis, such as: chinese patent publication nos. CN10178101, CN101781401, CN105885051 and CN102766261 all disclose a method for producing hydroxy silicone oil catalyzed by liquid acid, wherein CN10178101, CN101781401 and CN105885051 are a method for obtaining hydroxy silicone oil by catalytic polymerization with dimethyl cyclosiloxane (DMC) as raw material, acid anhydride and acid as catalyst, and the method is a common method for producing low viscosity hydroxy silicone oil at present; CN102766261 adopts sulfuric acid and phosphoric acid composite catalyst, and comprises dehydration and polymerization steps, so that a preparation method of hydroxyl silicone oil with high acetic anhydride conversion rate and low production cost is provided, but the method adopting a liquid acid catalytic system is adopted, alkali liquor is needed to neutralize in the production process, so that three wastes are generated, and in addition, the requirement on equipment under the acidic condition is high. Chinese patent publication numbers CN102408567 and CN106366318 both disclose a production method of hydroxyl silicone oil catalyzed by solid acid, wherein the hydroxyl silicone oil is prepared by using solid superacid as a catalyst, the preparation process is simple, but the catalyst is expensive, so the production cost is high.
The Chinese patent with publication number of CN102558559 discloses a method for synthesizing small molecular hydroxyl silicone oil by a resin catalyzed continuous method, and uses hexamethylcyclotrisiloxane, acetone, water and strong acid styrene cation exchange resin to synthesize low viscosity hydroxyl silicone oil, the method has high yield, however, the hydroxyl content of the obtained low viscosity hydroxyl silicone oil is only between 6 and 10 percent, and in addition, the price of the catalyst is relatively high, so that the production cost of the method is relatively high.
Chinese patent publication No. CN1821284A, CN 112625241a discloses a method for synthesizing low viscosity hydroxy silicone oil by using a base catalyst system, wherein CN1821284a synthesizes hydroxy silicone oil by using methyl cyclosiloxane as a raw material, toluene as a buffer, potassium hydroxide as a catalyst, and sulfuric acid as a neutralizing agent; CN 112625241a takes hexamethyl cyclotrisiloxane as raw material and one or more of sodium hydroxide, potassium hydroxide and tetramethyl ammonium hydroxide as catalyst, and transparent low-viscosity hydroxyl silicone oil is obtained through ring opening balancing, neutralization and desolventizing. The base catalyst system has the characteristics of good catalytic effect and low equipment requirement, but three wastes are still generated in the synthesis process.
In summary, the current methods for synthesizing the low-viscosity hydroxyl silicone oil (acid catalysis, base catalysis and resin catalysis) have respective advantages, but have the defects of three wastes, high requirements on equipment, high production cost and the like.
Disclosure of Invention
In order to overcome the defects, the invention provides a synthesis method of low-viscosity hydroxyl silicone oil.
The invention is realized by the following technical scheme:
the invention provides a synthesis method of low-viscosity hydroxyl silicone oil, which comprises the following steps:
s1, the mass ratio is (28-36): (18-22): (16-20): 1, a buffering agent, a reaction solvent and a first catalyst are mixed and stirred;
s2, heating to above 50 ℃, dissolving the hexamethylcyclotrisiloxane, continuously heating to 60-65 ℃, adding a second catalyst, and reacting for 1.8-2.2 hours at a temperature;
s3, adding an acetic acid solution to adjust the pH value to be neutral after the reaction is finished;
s4, extracting reaction liquid, separating an oil layer, performing low-boiling-point removal treatment on the oil layer, removing impurities, and filtering to obtain a finished product.
Further, the step S3 further includes the following steps: and (3) heating to above 90 ℃ and distilling the buffer under normal pressure to recover the buffer, wherein the reaction solvent remains after the oil layer is separated in the step S4, and the recovered buffer and the residual reaction solvent are used in the next synthesis.
Further, the method for removing low boiling in the step S4 is as follows: the oil layer is reduced in pressure and internal temperature of 85-95 ℃ for 1.8-2.2 hours, and low-boiling substances are removed to obtain crude oil.
Further, the impurity removing method in the step S4 is as follows: the crude oil is stirred with activated carbon at 46-54 ℃ for 1-2 hours.
Further, wherein the mass ratio of the hexamethylcyclotrisiloxane, the buffer, the reaction solvent, and the first catalyst is 32:20:18:1.
further, the first catalyst and the second catalyst are any one or more of potassium hydroxide, sodium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate and potassium hydrogen carbonate.
Further, the buffer is acetone or toluene.
Further, the reaction solvent is water, and the mass of the added water is 50-60% of the mass of the hexamethylcyclotrisiloxane, preferably 56.2%.
Further, in the step S2, the temperature is continuously raised to 62.5 ℃, and the reaction is kept for 2 hours.
The invention also provides low-viscosity hydroxyl silicone oil which is synthesized by adopting the synthesis method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for synthesizing low-viscosity hydroxyl silicone oil, which has mild reaction conditions and simple post-treatment, and the hydroxyl silicone oil synthesized by the method has no color and smell and low viscosity (20-30 mm) 2 S), high hydroxyl value (8-12%), and good stability; meanwhile, the buffer acetone, toluene and reaction solvent water used in the synthesis method can be reused, so that the production cost is effectively reduced, no three wastes are generated in the production process, and the concept of green chemistry is met; and more types of alkali are used as catalysts, so that the application of the method for synthesizing the low-viscosity hydroxyl silicone oil is further expanded, and the requirement of industrial mass production of the hydroxyl silicone oil can be met.
Detailed Description
The following describes in further detail the synthesis method of the low viscosity hydroxyl silicone oil according to the present invention with reference to specific examples. The advantages and features of the present invention will become more apparent from the following description.
The invention provides a synthesis method of low-viscosity hydroxyl silicone oil, which comprises the following steps:
s1, the mass ratio is (28-36): (18-22): (16-20): 1, a buffering agent, a reaction solvent and a first catalyst are mixed and stirred;
s2, heating to above 50 ℃ (including 50 ℃), dissolving the hexamethyl cyclotrisiloxane, continuously heating to 60-65 ℃, adding a second catalyst, and reacting for 1.8-2.2 hours at a temperature;
s3, adding an acetic acid solution to adjust the pH to 6.8-7.2 after the reaction is finished;
s4, extracting reaction liquid, separating an oil layer, performing low-boiling-point removal treatment on the oil layer, removing impurities, and filtering to obtain a finished product.
Preferably, the temperature of the step S2 is raised to 50 ℃.
Specifically, the first catalyst may not be added in the step S1.
Specifically, the step S3 further includes the following steps: the buffer was distilled off at atmospheric pressure at temperatures above 90 c (including 90 c) and recovered during which time hexamethylcyclotrisiloxane was distilled off, taking care to avoid clogging the condenser tube and the recovered buffer was used in the next synthesis.
Preferably, the buffer is distilled off at atmospheric pressure, with the temperature being increased to 90 ℃.
Specifically, in the step S4, after separating the oil layer, a reaction solvent remains, and the remaining reaction solvent is used in the next synthesis.
Specifically, the method for removing low boiling in step S4 includes: the oil layer is reduced (i.e. low-boiling-point removed) for 1.8-2.2 hours under reduced pressure and at an internal temperature of 85-95 ℃ to remove low-boiling-point substances and obtain crude oil.
Specifically, the reduced pressure is-0.095 MPa.
Preferably, the internal temperature is 90 ℃.
Preferably, the duration of the detachment is 2.0 hours.
Specifically, the method for removing impurities in step S4 includes: the crude oil is stirred with activated carbon at 46-54 ℃ for 1-2 hours.
Preferably, the temperature at the time of removing the impurities in the step S4 is 50 ℃.
Specifically, the mass fraction of the activated carbon is 1.0-2.0%, preferably 1.5%.
Preferably, in the step S1, the mass ratio of the hexamethylcyclotrisiloxane, the buffer, the reaction solvent and the first catalyst is 32:20:18:1.
specifically, the first catalyst and the second catalyst may be the same substance or may be different substances.
Specifically, the mass ratio of the first catalyst to the second catalyst is (112.5-137.5): 1.
specifically, the first catalyst and the second catalyst are any one or more of potassium hydroxide, sodium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate and potassium hydrogen carbonate.
Specifically, the buffer is acetone or toluene.
Specifically, the reaction solvent is water, and the mass of the added water is 56.2% of the mass of the hexamethylcyclotrisiloxane.
Preferably, in the step S2, the temperature is continuously raised to 62.5 ℃, and the reaction is kept for 2 hours.
The embodiment of the invention also provides low-viscosity hydroxyl silicone oil which is synthesized by adopting the synthesis method as claimed in any one of claims 1-7.
The following is a specific description of the embodiments:
example 1
Into a 2L three-neck flask, 450 g of hexamethyl cyclotrisiloxane, 225 g of acetone, 250 g of water and 12.5 g of disodium hydrogen phosphate are added, the temperature is raised to 50 ℃ to dissolve the hexamethyl cyclotrisiloxane, the system is divided into two phases, 0.1 g of potassium hydroxide is added continuously to 60 ℃, and the temperature is kept for 2.2 hours for reaction.
After 2 hours, the pH was adjusted to 7.2 by adding acetic acid solution. 219 g of acetone was distilled off at normal pressure and heated slowly to 90℃during which time hexamethylcyclotrisiloxane was distilled off, taking care to avoid clogging the condenser tube.
Extracting the reaction liquid by using a separating funnel, separating oil from water, removing low boiling point from an oil layer, and applying a water layer to the next reaction. The oil layer in the last step is reduced in pressure (-0.095 MPa) and is subjected to low temperature setting at 85 ℃ for 2.2 hours, and low-boiling impurities are removed. The activated carbon fine powder with the mass fraction of 1.5% is used for adsorption impurity removal, and is stirred for 2 hours at 46 ℃. Then, 380 g of the finished product was obtained by filtration, and the hydroxyl value was 11.3% as measured by the lithium aluminum hydride reduction method.
Example 2
Into a 2L three-necked flask, 450 g of hexamethylcyclotrisiloxane, 225 g of recovered acetone and 250 g of recovered water were added, the temperature was raised to 50 ℃ to dissolve hexamethylcyclotrisiloxane, the system was separated into two phases, 0.1 g of potassium hydroxide was added continuously to 60 ℃, and the reaction was continued for 2.2 hours.
After 2 hours, the pH was adjusted to 7.2 by adding acetic acid solution. Slowly heating to 90 ℃ and distilling the acetone at normal pressure, recovering the acetone, wherein the hexamethylcyclotrisiloxane is distilled off, and taking care to avoid blocking a condensing tube.
Extracting the reaction liquid by using a separating funnel, separating oil from water, removing low boiling point from an oil layer, and applying a water layer to the next reaction. The oil layer in the last step is reduced in pressure (-0.095 MPa) and is subjected to low temperature setting at 85 ℃ for 2.2 hours, and low-boiling impurities are removed. The activated carbon fine powder with the mass fraction of 1.5% is used for adsorption impurity removal, and is stirred for 2 hours at 46 ℃. Then, 395 g of the obtained product was filtered, and the hydroxyl value was 12.0% as measured by a lithium aluminum hydride reduction method.
Example 3
Into a 20L three-necked flask, 3500 g of hexamethylcyclotrisiloxane, 2750 g of toluene, 2000 g of water and 125 g of potassium hydrogencarbonate were charged. The temperature is raised to 50 ℃ to dissolve the hexamethylcyclotrisiloxane, the system is divided into two phases, the temperature is continuously raised to 65 ℃, 1 g of potassium hydroxide is added, and the reaction is kept for 1.8 hours.
After 2 hours, the pH was adjusted to 6.8 by adding acetic acid solution. Toluene was distilled off at normal pressure with a slow temperature rise to 90 ℃ and acetone was recovered during which time hexamethylcyclotrisiloxane was distilled off, taking care to avoid clogging the condenser tube.
Extracting the reaction liquid by using a separating funnel, separating oil from water, removing low boiling point from an oil layer, and applying a water layer to the next reaction. The oil layer in the last step is reduced in pressure (-0.095 MPa) and is subjected to low temperature setting at 95 ℃ for 1.8 hours, and low-boiling impurities are removed. The activated carbon fine powder with the mass fraction of 1.5% is used for adsorption impurity removal, and is stirred for 1 hour at 54 ℃. And then filtering to obtain 3941 g of finished product, wherein the hydroxyl value is 11.2% by using a lithium aluminum hydride reduction method.
Example 4
Into a 20L three-necked flask, 3500 g of hexamethylcyclotrisiloxane, 2750 g of recovered toluene and 2000 g of recovered water were added, the temperature was raised to 50 ℃ to dissolve hexamethylcyclotrisiloxane, the system was separated into two phases, 1 g of potassium hydroxide was added continuously to 65 ℃, and the reaction was continued for 1.8 hours.
After 2 hours, the pH was adjusted to 6.8 by adding acetic acid solution. Toluene was distilled off at normal pressure with a slow temperature rise to 90℃during which time hexamethylcyclotrisiloxane was distilled off, taking care to avoid clogging the condenser tube.
Extracting the reaction liquid by using a separating funnel, separating oil from water, removing low boiling point from an oil layer, and applying a water layer to the next reaction. The oil layer in the last step is reduced in pressure (-0.095 MPa) and is subjected to low temperature setting at 95 ℃ for 1.8 hours, and low-boiling impurities are removed. The activated carbon fine powder with the mass fraction of 1.5% is used for adsorption impurity removal, and is stirred for 1 hour at 54 ℃. And then filtering to obtain 3950 g of finished product, wherein the hydroxyl value is 11.5% by using a lithium aluminum hydride reduction method.
The lithium aluminum hydride reduction method comprises the following specific steps:
preparing a lithium aluminum hydride standard solution: about 0.2 g of lithium aluminum hydride is taken in a reactor, 25 ml of anhydrous diethylene glycol dimethyl ether is added, stirred and dissolved, and the mixture is clarified for standby.
Sample arrangement: accurately weighing 0.2000-0.4000 g of sample in a 10 ml volumetric flask, adding anhydrous diethylene glycol dimethyl ether to the scale, and completely dissolving for later use.
And accurately sucking 10-30 microliters of sample solution by using a syringe, injecting the sample solution into a reactor, reacting for 3 minutes, collecting generated hydrogen, and calculating to obtain the hydroxyl value of the sample.
The above description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention, and any alterations and modifications made by those skilled in the art based on the above disclosure shall fall within the scope of the appended claims.
Claims (10)
1. A synthesis method of low-viscosity hydroxyl silicone oil is characterized in that: the method comprises the following steps:
s1, the mass ratio is (28-36): (18-22): (16-20): 1, a buffering agent, a reaction solvent and a first catalyst are mixed and stirred;
s2, heating to above 50 ℃, dissolving the hexamethylcyclotrisiloxane, continuously heating to 60-65 ℃, adding a second catalyst, and reacting for 1.8-2.2 hours at a temperature;
s3, adding an acetic acid solution to adjust the pH to 6.8-7.2 after the reaction is finished;
s4, extracting reaction liquid, separating an oil layer, performing low-boiling-point removal treatment on the oil layer, removing impurities, and filtering to obtain a finished product.
2. The synthesis method according to claim 1, wherein: the step S3 further comprises the following steps: and (3) heating to above 90 ℃ and distilling the buffer under normal pressure to recover the buffer, wherein the reaction solvent remains after the oil layer is separated in the step S4, and the recovered buffer and the residual reaction solvent are used in the next synthesis.
3. The synthesis method according to claim 1, wherein: the method for removing low boiling point in the step S4 comprises the following steps: the oil layer is reduced in pressure and internal temperature of 85-95 ℃ for 1.8-2.2 hours, and low-boiling-point substances are removed.
4. The synthesis method according to claim 1, wherein: the impurity removing method in the step S4 comprises the following steps: stirring with activated carbon at 46-54 deg.C for 1-2 hr.
5. The synthesis method according to claim 1, wherein: wherein the mass ratio of the hexamethylcyclotrisiloxane, the buffer, the reaction solvent and the first catalyst is 32:20:18:1.
6. the synthesis method according to claim 1, wherein: the first catalyst and the second catalyst are any one or more of potassium hydroxide, sodium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate and potassium hydrogen carbonate.
7. The synthesis method according to claim 1, wherein: the buffer is acetone or toluene.
8. The synthesis method according to claim 1, wherein: the reaction solvent is water, and the mass of the added water is 56.2% of the mass of the hexamethylcyclotrisiloxane.
9. The synthesis method according to claim 1, wherein: and in the step S2, the temperature is continuously increased to 62.5 ℃, and the reaction is kept for 2 hours.
10. A low viscosity hydroxy silicone oil characterized in that: synthesized by the synthesis method according to any one of claims 1 to 9.
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| CN202311656671.9A Pending CN117487164A (en) | 2023-12-06 | 2023-12-06 | Synthesis method of low-viscosity hydroxyl silicone oil |
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